Intramolecular Electron Transfer in Pentaammineruthenium(III)-Modified Cobaltocytochrome c

Inorganic Chemistry

Volumn 35, Issue 20, 1996, Pages 5893-5901

  Sun, Ji ^a,b   Su, Chang ^a,c   Wishart, James F ^a  

^a BROOKHAVEN NATIONAL LABORATORY   (United States)

^b GEN Inc   (United States)

^c HOFFMANN LA ROCHE INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0005049342     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic960715w     Document Type: Article

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48. 45b suggest that electronic coupling is stronger for low-spin cobalt than for low-spin iron, due to orbital occupancy/symmetry and radial extent differences. It is difficult to be quantitative about transferring the above results to a c-type heme environment. One difference is that the heme, histidine, and methionine ligands have π-interactions with the central metal, which may reduce the difference between iron and cobalt. If, however, coupling is stronger in the cobalt case, then the estimated reorganization energy of 2.4 eV for CoCyt c might be a lower limit. This coupling question affects the inter- and intramolecular redox reactions in the same way, so subsequent inferences (vide infra) about the integrity of the intramolecular ET "pathway" upon metal substitution are not affected,
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